Process for trichromatic dyeing or printing of natural and synthetic polyamide material with fibre-reactive formazan dyes and fibre-reactive azo dyes

ABSTRACT

The fibre-reactive formazan dyes of the formula ##STR1## where B is an aliphatic or sulfo-free aromatic bridge member, R is α,β-dihalopropionyl, α-haloacryloyl or haloacetyl, T 1  is halogen, X is halogen, C 1  -C 4  alkyl, C 1  -C 4  alkoxy, cyano or nitro, Y is --CO-- or --SO 2  --, Z is nitrogen or --C--T 2 , T 2  is halogen, hydrogen, C 1  -C 4  alkylthio, cyano, formyl or C 1  -C 4  alkylsulfonyl, m is 1, 2 or 3, n is 0, 1 or 2, q is 0 or 1, and r and s are each either 0 or 1 but never the same as each other, produce dyeings having good fastness properties on nitrogen-containing or hydroxyl-containing fibre materials.

This is a divisional of application Ser. No. 374,320 filed on Jun. 29,1989, now U.S. Pat. No. 4,994,562 issued Feb. 19, 1991.

The present invention relates to novel fibre-reactive formazan dyes, toprocesses for preparing them and to the use of these dyes for dyeing andprinting fibre materials.

The present invention provides fibre-reactive formazan dyes of theformula ##STR2## where B is an aliphatic or sulfo-free aromatic bridgemember, R is α,β-dihalopropionyl, α-haloacryloyl or haloacetyl, T₁ ishalogen, X is halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, cyano or nitro, Y is--CO-- or --SO₂ --, Z is nitrogen or --C--T₂, T₂ is halogen, hydrogen,C₁ -C₄ alkylthio, cyano, formyl or C₁ -C₄ alkylsulfonyl, m is 1, 2 or 3,n is 0, 1 or 2, q is 0 or 1, and r and s are each either 0 or 1 butnever the same as each other.

An aliphatic bridge member B in the formula (1) is C₁ -C₈ alkylene, inparticular C₁ -C₆ alkylene, which may be substituted in the alkylene,for example by halogen, such as fluorine, chlorine or bromine, or by C₁-C₄ -alkoxy, such as methoxy or ethoxy.

An aromatic bridge member B in the formula (1) is naphthylene or inparticular phenylene. Examples of substituents for naphthylene andphenylene are:

alkyl groups of 1 to 8, preferably 1 to 4, carbon atoms, e.g. methyl,ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, hexylor octyl, alkoxy groups of 1 to 8 carbon atoms, in particular 1 to 4carbon atoms, e.g. methoxy, ethoxy, propoxy, isopropoxy or butoxy,acylamino groups such as alkanoylamino groups of 2 to 8 carbon atoms andalkoxycarbonylamino groups of 2 to 8 carbon atoms e.g. acetylamino,propionylamino, methoxycarbonylamino, ethoxycarbonylamino orbenzoylamino, C₅ -C₇ cycloalkylcarbonyl, benzoyl, amino, mono- ordialkylamino of 1 to 8 carbon atoms in the alkyl radical, phenylamino,alkoxycarbonyl of 1 to 8 carbon atoms in the alkoxy radical, C₅ -C₇cycloalkylaminosulfonyl, nitro, cyano, trifluoromethyl, halogen, such asfluorine, bromine or in particular chlorine, sulfamoyl, sulfamoyl whichis monosubstituted or disubstituted on the nitrogen atom by C₁ -C₄alkyl, C₅ -C₇ cycloalkyl or phenyl, carbamoyl, ureido, hydroxyl, C₁ -C₈alkylsulfonyl, C₁ -C₈ alkylaminosulfonyl, unsubstituted or C₁ -C₄alkyl-substituted phenylsulfonyl, carboxyl, sulfomethyl, sulfato orthiosulfato, and also phenyl, naphthyl, phenoxy, phenoxysulfonyl andphenylaminosulfonyl, which phenyl or naphthyl radicals may be furthersubstituted by the abovementioned substituents.

An α,β-dihalopropionyl R in the formula (1) is for exampleα,β-dibromopropionyl, α,β-dichloropropionyl, α-chloro-β-bromopropionylor α-bromo-β-chloropropionyl.

An α-haloacryloyl R in the formula (1) is for example α-bromoacryloyl orα-chloroacryloyl.

A haloacetyl R in the formula (1) is bromoacetyl or chloroacetyl.

Halogen T₁ in the formula (1) is for example fluorine or in particularchlorine.

Halogen T₂ in the formula (1) is for example fluorine or in particularchlorine.

A C₁ -C₄ alkylthio T₂ in the formula (1) is for example methylthio,ethylthio, propylthio, isopropylthio, butylthio, isobutylthio,sec-butylthio or tert-butylthio.

A C₁ -C₄ alkylsulfonyl T₂ is for example methylsulfonyl, ethylsulfonylor isopropylsulfonyl.

Halogen X in the formula (1) is for example fluorine or bromine or inparticular chlorine.

A C₁ -C₄ alkyl X in the formula (1) is for example methyl, ethyl,propyl, isopropyl, butyl, isobutyl, sec-butyl or in particulartert-butyl.

A C₁ -C₄ alkoxy X in the formula (1) is for example methoxy, ethoxy,propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy or tert-butoxy.

Preference is given to dyes of the formula (1) where m is 2. Preferenceis further given to dyes of the formula (1) where q is 1.

Preference is likewise given to dyes of the formula (1) where X ishalogen, in particular chlorine; particular preference is given to dyesof the formula (1) where m is 2, q is 1 and X is chlorine.

Preference is further given to dyes of the formula (1) where B is--(CH₂)_(p) -- or ##STR3## p is 1, 2, 3, 4, 5 or 6, and X₁ is hydrogenor a substituent other than sulfo; more particularly, B is as definedabove, m is 2, q is 1 and X is chlorine. The substituent X₁ can have thesame meanings as the abovementioned substituents on a phenylene B.

Preferably, n in the formula (1) is 0 or 1, in particular together withthe abovementioned preferred meanings of m, q, X and/or B.

Preferably, T₁ in the formula (1) is fluorine or in particular chlorineand Z is --C--F or --C--Cl or in particular nitrogen; in particular, T₁and Z have the abovementioned meanings together with the abovementionedpreferred meanings of m, n, q, X and/or B.

Particular preference is given to the dyes of the formula ##STR4## whereB is phenylene, R is an α,β-dihalopropionyl, α-haloacryloyl orhaloacetyl radical where the halogen is bromine and/or chlorine, T₁ isfluorine or in particular chlorine, X is chlorine, Y is --CO-- or --SO₂--, n is 0 or 1, r is 0 or 1 and s is 0 or 1.

Very particular preference is given to the dyes of the formula ##STR5##where R, T₁, Y, r and s are as defined under the formula (2).

Of the very particularly preferred dyes of the formula (3), the dyes ofthe formulae ##STR6## where in the formulae (4) and (5) R isα,β-dibromopropionyl, α-bromoacryloyl or chloroacetyl, the sulfo groupis bonded to the benzo ring A in the 4- or 5-position, --NH--R is bondedto the benzo ring D in the 3- or 4-position, T₁ in the formula (4) isfluorine and in particular chlorine, and Y in the formula (5) is --CO--or --SO₂ --, are very particularly important.

The present invention further provides a process for preparing the dyesof the formula (1), which comprises reacting a compound of the formula##STR7## where X, m, n and q are as defined under the formula (1), witha compound which introduces the radical of the formula ##STR8## where B,R, Y, T₁, Z, r and s are as defined under the formula (1), or condensingan amine of the formula (6), where X, m, n and q are as defined underthe formula (1) with a compound of the formula ##STR9## where Z and T₁are as defined under the formula (1), and each Hal is a halogen atom, inparticular a fluorine or chlorine atom, and then reacting thecondensation product with a compound which introduces the radical

    --NH--B--NH--R                                             (9)

where B and R in the formula (9) are as defined under the formula (1).

The compound introducing the radical of the formula (7) is preferably acorresponding halide, in particular a chloride or fluoride. Specificexamples are: ##STR10##

In a preferred embodiment of the process according to the invention, acompound of the formula (6) is first condensed with a compound of theformula ##STR11## where Z and T₁ are as defined under the formula (1)and each Hal is a halogen atom, in particular a fluorine or chlorineatom, and the condensation product is then reacted with a compoundintroducing the radical of the formula

    --NH--B--NH--R                                             (9)

where B and R in the formula (9) are as defined under the formula (1).Examples of compounds of the formula (8) are: cyanuric chloride,cyanuric fluoride and 2,4,6-trifluoro-5-chloropyrimidine. Examples ofcompounds introducing the radical of the formula (9) are:3'-amino-2,3-dibromopropionylanilide,4'-amino-2,3-dibromopropionylanilide, 3'-amino-2-bromoacryloylanilide,4'-amino-2-bromoacryloylanilide, 3'-aminochloroacetanilide and4'-aminochloroacetanilide.

In a likewise preferred embodiment of the process according to theinvention, a compound of the formula (6) is reacted with a compoundintroducing the radical of the formula

    --Y--B--NH--R                                              (10)

where Y, B and R are as defined under the formula (1). Examples ofcompounds which introduce the radical of the formula (10) arecorresponding acid halides, preferably acid chlorides such as ##STR12##

The compounds of formula (10), which include a detachable group,preferably a halogen atom, and which conform to the formula

    Z--Y--B--NH--R                                             (10a)

form a further part of the subject-matter of the present invention. Z inthe formula (10a) is a detachable group, in particular a halogen atom,preferably chlorine. Y, B and R are as defined in the formula (1).Preferably, B and R have the abovementioned preferred meanings.

The compounds of the formula (10a) are prepared by condensing forexample a compound of the formula

    HO--Y--B--NH.sub.2                                         ( 10b)

where Y and B are as defined under the formula (1) with a compound whichintroduces the radical R, and the condensation product is then reactedwith a compound which introduces the group Z.

In particular, use is made of a compound of the formula (10b) where B is--(CH₂)_(p) -- or ##STR13## p is 1, 2, 3, 4, 5 or 6, and X₁ is hydrogenor a substituent other than sulfo.

Examples of compounds which introduce the radical R are2,3-dibromopropionyl chloride or 2-bromoacryloyl chloride.

An example of a compound which introduces the group Z is thionylchloride.

In a further very particularly preferred embodiment of the novel processfor preparing the dyes of the formula (1), a compound of the formula (6)is reacted with a compound of the formula

    Z--Y--B--NHCOCH.sub.3                                      ( 10c)

where Z, Y and B are as defined under the formula (10a), the reactionproduct then hydrolyses in the presence of a base, such as NaOH, and thehydrolysed product is then condensed with a compound which introducesthe radical R.

Suitable compounds of the formula (10c) are for example: ##STR14##Examples of compounds which introduce the radical R are2,3-dibromopropionyl chloride, 2-bromoacryloyl chloride andα-chloroacetyl chloride.

The preparation of the dyes of the formula (1) having a dihalopropionylgroup can be followed by an elimination reaction. For example, the dyeof the formula (1) which contains a dihalopropionyl group can be treatedunder alkaline conditions, such as sodium hydroxide, to eliminatehydrogen halide and convert the dihalopropionyl radical into ahaloacryloyl radical.

The condensation of the amine of the formula (6) with compound whichintroduces the radical of the formula (7), or the condensation of theamine of the formula (6) with the compound of the formula (8) and thesubsequent reaction with the compound which introduces the radical (9),and the condensation of the amine of the formula (6) with the compoundwhich introduces the radical of the formula (10) are each preferablycarried out in aqueous solution, emulsion or suspension at a lowtemperature, for example at 0° to 40° C. and at a weakly acid, neutralor weakly alkaline pH. Advantageously, the hydrogen halide set free inthe course of the condensation is continuously neutralized by additionof aqueous alkali metal hydroxides, carbonates or bicarbonates.

In a preferred embodiment of the process according to the invention, useis made of an amine of the formula (6) where m is 2.

In a further preferred embodiment of the process according to theinvention, use is made of an amine of the formula (6) where q is 1.

In a likewise preferred embodiment of the process according to theinvention, use is made of an amine of the formula (6) where X ishalogen, in particular chlorine, in particular of an amine of theformula (6) where X is chlorine, m is 2 and q is 1, together with acompound which introduces the radical of the formula (7).

In a further preferred embodiment of the process according to theinvention, use is made of a compound which introduces the radical of theformula (7), (8) or (9) where B is --(CH₂)_(p) -- or ##STR15## p is 1,2, 3, 4, 5 or 6, and X₁ is hydrogen or a substituent other than sulfo.

More particularly, use is made of an amine of the formula (6) where m is2, q is 1 and X is chlorine together with a compound which introducesthe radical of the formula (7) where B has the preferred meaning givenabove. Preference is also given to using amines of the formula (6) wheren is 0 or 1; in particular together with the abovementioned preferredmeanings of the radicals m, q and X.

Preference is further given to compounds of the formula (7) or of theformula (8) where T₁ is fluorine or in particular chlorine and Z is--C--F or --C--Cl or in particular a nitrogen.

In a particularly preferred embodiment of the novel process forpreparing dyes of the formula (2), a compound of the formula ##STR16##where X and n are as defined under the formula (2), is either condensedwith a compound of the formula (8) and afterwards the condensationproduct is reacted with a compound which introduces the radical of theformula (9), or with a compound which introduces the radical of theformula (10), B, R, T₁, X, Y and n being as defined under the formula(2).

In a very particularly preferred embodiment of the novel process forpreparing the dyes of the formula (3), an amine of the formula ##STR17##is either condensed with cyanuric chloride or cyanuric fluoride andafterwards the condensation product is reacted with a compound whichintroduces the radical of the formula (9), or is reacted with a compoundwhich introduces the radical of the formula (10), R and Y being asdefined under the formula (3).

The particularly important dyes of the formula (4) are prepared bycondensing an amine of the formula ##STR18## where the sulfo group isbonded to the benzo ring A in the 4- or 5-position, with cyanuricchloride or cyanuric fluoride and then reacting the condensation productwith a compound of the formula ##STR19## where R is as defined underformula (4) and --NHR is bonded to the benzo ring D in the 3- or4-position.

The particularly important dyes of the formula (5) are prepared byreacting an amine of the formula (13) with a compound of the formula##STR20## where Hal is halogen, in particular chlorine, Y and R are asdefined under the formula (5) and --NH--R is bonded to the benzo ring Din the 3- or 4-position.

The compounds of the formula (6) are known per se or can be preparedsimilarly to known compounds. For the preparation of the coppercomplexes of the tetradentate formazans, reference may be made to K.Venkataraman, The Chemistry of Synthetic Dyes, Volume VI, pages 287 to297, Academic Press New York and London (1972), and UllmannsEncyklopadie der technischen Chemie, Volume 11, pages 714 to 718, VerlagChemie (1976).

The compounds which introduce the radical of the formula (7), (9) or(10) and the compounds of the formula (8) are likewise known per se orcan be prepared similarly to known compounds.

The dyes of the formula (1) are suitable for dyeing and printing a widerange of fibre materials, in particular textile fibre materials, forexample silk, fibre materials made of cellulose and in particular wool,synthetic polyamide fibre materials, for example nylon-6- and nylon 6,6,and leather. The dyes of the formula (1) give level dyeings in blueshades having good all round fastness properties, in particular good wetfastness, such as wet rub fastness, and good light fastness.Furthermore, the dyes of formula (1) are very highly compatible withother reactive dyes. The abovementioned textile material can be presentin a very wide range of processing forms, for example as yarn, wovenfabric or knitted fabric.

It is to be noted that the dyes of the formula (1) according to theinvention show high reduction stability, have good dyeingcharacteristics, give a high rate of fixation and high levelness in thefibre and the piece, and do not show any dichroism.

The novel dyes of the formula (1) which contain at least one sulfo groupare present either in the form of their free acid or preferably as asalt thereof. Examples of possible salts are alkali metal, alkalineearth metal or ammonium salts or the salts of an organic amine. Examplesare the sodium, lithium, potassium or ammonium salts and the salt oftriethanolamine.

It is further to be noted that the novel dyes of the formula (1) aresuitable for the trichromatic dyeing and printing of natural orsynthetic polyamide fibre materials together with a fibre-reactiveyellow- or orange-dyeing dye and a fibre-reactive red-dyeing dye.

Trichromatic relates to the additive mixture of suitably selectedyellow- or orange-, red- and blue-dyeing dyes with which any desiredshade of the visible spectrum can be matched through a suitable choiceof the mixing ratios.

The dyes to be used in the trichromatic process should combine a uniformcolour build-up with a constant shade at various concentrations and goodcompatibility.

The present invention accordingly provides a process for thetrichromatic dyeing or printing of natural and synthetic polyamide fibrematerials with mixtures of fibre-reactive dyes, which comprises using ablue-dyeing dye of the formula (1) together with a yellow- ororange-dyeing sulfo-containing reactive dye and a red-dyeingsulfo-containing reactive dye.

Use is made in particular of fibre-reactive sulfo-containing yellow- ororange- and red-dyeing azo dyes where the fibre-reactive group ispreferably a halotriazine or halopyrimidine group or a group of thealiphatic series.

A halopyrimidine or aliphatic fibre-reactive group is preferablydifluorochloropyrimidinyl, in particular2,4-difluoro-5-chloropyrimidinyl, on the one hand orα,β-dihalopropionyl, in particular α,β-dibromopropionyl, orα-haloacryloyl, in particular α-bromoacryloyl on the other.

Examples of yellow- or orange-dyeing sulfo-containing fibre-reactivedyes are the following: ##STR21##

Examples of red-dyeing sulfo-containing fibre-reactive dyes are thefollowing: ##STR22## where acyl is for example acetyl or substituted orunsubstituted benzoyl.

The fused rings indicated by dots represent alternatively possiblenaphthalene systems. ##STR23##

In the foregoing formulae, R₁ is a fibre-reactive radical, in particulara fibre-reactive radical of the halotriazine or halopyrimidine series orof the aliphatic series, R₁ preferably being difluorochloropyrimidinylor α,β-dihalopropionyl or α-bromoacryloyl. Particularly preferably, R₁is 2,4-difluoro-5-chloropyrimidin-6-yl, α,β-dibromopropionyl orα-bromoacyloyl.

In the novel process for the trichromatic dyeing or printing of naturaland synthetic polyamide fibre materials, the blue-dyeing dyes used arethose mentioned above, in particular those of the formulae (2) and (3),very particularly preferably the dyes of the formulae (4) and (5).

Particularly preferred yellow- or orange-dyeing dyes are: ##STR24##

Particularly preferred red-dyeing dyes are: ##STR25##

The yellow- or orange- and red-dyeing dyes used in the novel process fortrichromatic dyeing or printing are known or can be prepared similarlyto known dyes. The dyes are present either in the form of their freesulfonic acid or preferably as a salt thereof, in which case it ispossible to use the same salts as indicated for the dyes of the formula(1).

The amounts in which the dyes of the formula (1) and the yellow- ororange- and red-dyeing fibre-reactive dyes are used in the dyebaths orprint pastes can vary within wide limits, depending on the desired depthof shade; in general, amounts of from 0.01 to 10 per cent by weight, inparticular of 2 to 10 per cent by weight, based on the material to bedyed or the print paste, have proved to be advantageous.

Preference is given to using in the process according to the inventionfibre-material made of natural polyamides, in particular wool.

Special equipment is not required in the process according to theinvention. It is possible to use the customary dyeing and printingmachines, for example for loose fibre, fluffing, hanks, packages, piecegoods and carpets.

As well as the reactive dye aqueous dyebaths may contain assistants, inparticular levelling assistants. Levelling assistants are used in anamount of 0.3 to 3 per cent by weight, based on the fibre material.

Further assistants which may be present in the dyebaths are mineralacids, such as sulfuric acid, sulfamic acid or phosphoric acid, organicacids, advantageously lower aliphatic carboxylic acids, such as formicacid, acetic acid or maleic acid. The acids are used in particular toadjust the pH of the liquors to be used according to the invention.

Preferably, the pH of 3 to 6 is set with an organic acid, in particularformic acid or acetic acid.

Preference is given to dyeing at a pH of 4 to 6, in particular 4.2 to5.5.

It is also possible for the dyeing liquor to contain various salts, inparticular ammonium salts or alkali metal salts, for example ammoniumsulfate or sodium sulfate, as assistants.

The liquor ratio can be varied within a wide range, for example from 6:1to 80:1, preferably from 10:1 to 50:1.

Dyeing takes place from an aqueous liquor by the exhaust method, forexample at a temperature between 80° and 105° C. or 110° C. using aformaldehyde-eliminating wool preservative, preferably between 98° and103° C.

The dyeing time is in general 30 to 90 minutes.

In a particularly preferred embodiment of the process according to theinvention, the dyeing liquor, having been used for dyeing at preferably98° to 103° C., is cooled down to about 75° to 90° C. and the pH isadjusted to 8 to 9, preferably to about 8.5. The pH can be adjusted bycustomary means, for example alkali metal hydroxide solutions and inparticular by means of aqueous ammonia solution of customaryconcentration, containing for example 25 percent by weight of ammonia.

In the Examples, parts are by weight. The temperatures are degreesCelsius. Parts by weight bear the same relation to parts by volume asthat between gram and cubic centimeter.

EXAMPLE 1

13.24 parts of the dye of the formula (101) ##STR26## are taken up in200 parts of water, admixed with 0.6 part of disodium hydrogenphosphateand heated to 40°, when the sodium hydroxide solution is added to pH 6.5and a clear solution forms. After cooling to 0°-2° a solution of 3.9parts of cyanuric chloride in 25 parts of acetone is added dropwise inthe course of 2-3 minutes, during which the pH is maintained at 6.25with sodium hydroxide solution.

After the reaction has ended, a solution of 7.72 parts of4'-amino-2,3-dibromopropionylanilide in 1:2 water/acetone is addeddropwise at 0°-5° in the course of 5 minutes, during which the pH iskept at a constant 6.25 with sodium hydroxide solution. After stirringovernight, the dye is filtered off with suction, washed with sodiumchloride solution and dried at 60°-70°. 25.1 parts are obtained of a dyeof the formula (102) which dyes wool in fast blue shades. ##STR27##

EXAMPLE 2

3 parts of the dye of the formula (102) of Example 1 are dissolved in 50parts of water. The solution is adjusted to pH 12 with sodium hydroxidesolution and maintained at 40° for 2 hours. After cooling, the pH isreduced to 7, sodium chloride is added, and the dye is filtered off withsuction, washed with sodium chloride solution and dried at 60°-70°. 3.1g are obtained of the dye of the formula (103) which dyes wool in fastblue shades. ##STR28##

EXAMPLE 3

Example 1 is repeated, except that the dye of the formula (101) isreplaced by an equimolar amount of the dye of the formula ##STR29##affording a dye of the formula (105) which dyes wool in fast blueshades. ##STR30##

EXAMPLE 4

Example 2 is repeated, except that the dye of the formula (102) isreplaced by the dye of the formula (105) of Example 3, affording the dyeof the formula (106) which dyes wool in fast blue shades. ##STR31##

EXAMPLES 5 TO 8

The procedure of Examples 1 to 4 is repeated, except that4'-amino-2,3-dibromopropionylanilide is replaced by an equimolar amountof 3'-amino-2,3-dibromopropionylanilide, affording the dyes listed incolumn 2 of Table 1 which dye wool in the shades indicated in column 3.

                                      TABLE 1                                     __________________________________________________________________________                                                               Hue                                                                           on                 Ex.                                                                              Dye                                                     wool               __________________________________________________________________________        ##STR32##                                              blue               6                                                                                 ##STR33##                                              blue               7                                                                                 ##STR34##                                              blue               8                                                                                 ##STR35##                                              blue               __________________________________________________________________________

EXAMPLE 9

6.62 parts of the dye of the formula (104) of Example 3 are dissolved in50 parts of water at pH 7 by adding hydrochloric acid. After 0.84 partof sodium bicarbonate has been added, a solution of 6.1 parts of4-(2',3'-dibromopropionamido)benzenesulfonyl chloride (prepared byreacting sulfanilic acid with 2,3-dibromopropionyl chloride andsubsequent conversion into the corresponding sulfonyl chloride withthionyl chloride in the presence of dimethylformamide) in 25 parts ofacetone is added dropwise at room temperature in the course of 10-15minutes, during which the pH is maintained at 7 with sodium hydroxidesolution. After one hour at 30° and stirring at room temperature, thedye is precipitated by the addition of sodium chloride, filtered offwith suction, washed with sodium chloride solution and dried at 60°-70°.11 parts are obtained of the dye of the formula (111) which dyes wool infast blue shades. ##STR36##

EXAMPLE 10

Example 9 is repeated, except that a solution of 6.62 parts of the dyeof the formula (101) of Example 1 in 100 parts of water and 0.3 part ofdisodium hydrogenphosphate are used, affording 11 parts of a dye of theformula (112) which dyes wool in fast blue shades. ##STR37##

EXAMPLES 11 AND 12

5.5 parts of the dye of the formula (111) or (112) are stirred in 100parts of water in the presence of sodium hydroxide solution at a pH of12 to 12.5 and at 0° to 5° for one hour. The suspension is then broughtto pH 7 with hydrochloric acid, and sodium chloride is added. The dye isfiltered off with suction, washed with sodium chloride solution anddried at 60°-70°. This gives 5.3 parts of the dye of the formula (113)or 5.6 parts of the dye of the formula (114), which both dye wool infast blue shades. ##STR38##

EXAMPLES 13 TO 16

The procedure of Examples 9 to 12 is repeated, except that the 6.1 partsof 4-(2',3'-dibromopropionamido)benzenesulfonyl chloride are replaced byan equimolar amount of 3-(2',3'-dibromopropionamido)benzenesulfonylchloride, affording the dyes indicated in column 2 of Table 2 which dyewool in the shades indicated in column 3.

                                      TABLE 2                                     __________________________________________________________________________    Ex. Dye                                                Hue on                 __________________________________________________________________________                                                           wool                   13                                                                                 ##STR39##                                         blue                   14                                                                                 ##STR40##                                         blue                   15                                                                                 ##STR41##                                         blue                   16                                                                                 ##STR42##                                         blue                   __________________________________________________________________________

EXAMPLE 17

1.7 parts of the dye of the formula (104) in Example 3 are dissolved in50 parts of water at pH 7 by adding hydrochloric acid, and a littledisodium hydrogenphosphate is added. To this solution is added 1 part of3-(2',3'-dibromopropionamido)benzoyl chloride (prepared by reacting3-aminobenzoic acid with 2,3-dibromopropionyl chloride and subsequentconversion to the corresponding benzoyl chloride with thionyl chloridein the presence of dimethylformamide) dissolved in acetone, addeddropwise in the course of 5 minutes. After stirring overnight at aconstant pH of 7, maintained with sodium hydroxide solution, sodiumchloride is added, and the dye is filtered off, washed with sodiumchloride solution and dried at 60°-70°. 2.5 parts are obtained of a dyeof the formula (119) which dyes wool in fast blue shades. ##STR43##

EXAMPLE 18

Example 17 is repeated, except that a dye of the formula (101) ofExample 1 is used, affording 2.8 parts of a dye of the formula (120)which dyes wool in fast blue shades. ##STR44##

EXAMPLES 19 AND 20

The procedure of Examples 11 and 12 is repeated, except that the dyes ofthe formulae (111) and (112) are replaced by the dyes of the formulae(119) and (120), affording dyes of the formulae (121) and (122) whichboth dye wool in fast blue shades. ##STR45##

EXAMPLES 21 TO 24

The procedure of Examples 17 to 20 is repeated, except that the3-(2',3'-dibromopropionamido)benzoyl chloride is replaced by anequimolar amount of 4-(2',3'-dibromopropionamido)benzoyl chloride,affording the dyes indicated in column 2 of Table 3 which dye wool inthe shades indicated in column 3.

                                      TABLE 3                                     __________________________________________________________________________    Ex. Dye                                                Hue on                 __________________________________________________________________________                                                           wool                   21                                                                                 ##STR46##                                         blue                   22                                                                                 ##STR47##                                         blue                   23                                                                                 ##STR48##                                         blue                   24                                                                                 ##STR49##                                         blue                   __________________________________________________________________________

EXAMPLE 25

6.62 parts of the dye of the formula (101) are dissolved and reactedwith cyanuric chloride, both steps being carried out as described inExample 1. A solution of 2.9 parts of 3'-amino-2-bromoacryloylanilide in40 parts of acetone is then added dropwise at 0°-5° and at a pH of 6.5in the course of 10 minutes. After stirring overnight, sodium chlorideis added, and the dye is filtered off and washed with sodium chloridesolution. Drying at 60°-70° leaves 12.6 parts of the dye of the formula(108).

EXAMPLE 26

Example 25 is repeated, except that the dye of the formula (101) isreplaced by the dye of the formula (104), affording the dye of theformula (110).

EXAMPLES 27 AND 28

The procedure of Examples 25 and 26 is repeated, except that the3'-amino-2-bromoacryloylanilide is replaced by an equimolar amount of4'-amino-2-bromoacryloylanilide, affording dyes of the formulae (103)and (106).

EXAMPLES 29 TO 36

The procedure of Examples 1 to 8 is repeated, except that the cyanuricchloride is replaced by an equimolar amount of cyanuric fluoride,affording the dyes indicated in column 2 of Table 4 which dye wool inthe shades indicated in column 3.

                                      TABLE 4                                     __________________________________________________________________________                                                                Hue                                                                           on                Ex.                                                                              Dye                                                      wool              __________________________________________________________________________    29                                                                                ##STR50##                                               blue              30                                                                                ##STR51##                                               blue              31                                                                                ##STR52##                                               blue              32                                                                                ##STR53##                                               blue              33                                                                                ##STR54##                                               blue              34                                                                                ##STR55##                                               blue              35                                                                                ##STR56##                                               blue              36                                                                                ##STR57##                                               blue              __________________________________________________________________________

EXAMPLE 37

To a suspension of 3.22 parts of 4'-amino-2,3-dibromopropionylanilide in25 parts of water is added dropwise a solution of 2.02 parts of cyanuricchloride in 30 parts of acetone at 0°-2° and a pH of 6-6.5. After thereaction has ended, a solution of 6 parts of the dye of the formula(104) in 50 parts of water (brought to pH 7 with hydrochloric acid) isadded at 5° in the course of 15 minutes, during which the pH ismaintained at a constant 6.25 with sodium chloride solution. Afterstirring overnight at room temperature, sodium chloride is added. Thedye is filtered off with suction, washed with sodium chloride and driedat 60°-70°. 10.8 parts are obtained of the dye of the formula (105).

EXAMPLES 38 TO 44

Example 37 is repeated, except that the4'-amino-2,3-dibromopropionylanilide is replaced by an equimolar amountof 3'-amino-2,3-dibromopropionylanilide or4'-amino-2-bromoacryloylanilide or 3'-amino-2-bromoacryloylanilidetogether with a dye of the formula (104) or an equimolar amount of thedye of the formula (101), affording the corresponding dyes of theformulae (102), (103), (106), (107), (108), (109) and (110).

EXAMPLES 45 TO 52

The procedure of Examples 1, 3, 5, 7, 29, 31, 33 and 35 is repeated,except that the 3'- or 4'-amino-2,3-dibromopropionylanilide is replacedby an equimolar amount of 3'- or 4'-aminochloroacetanilide, affordingthe dyes indicated in column 2 of Table 5 which dye wool in the shadesindicated in column 3.

                                      TABLE 5                                     __________________________________________________________________________                                                          Hue                                                                           on                      Ex.                                                                              Dye                                                wool                    __________________________________________________________________________    45                                                                                ##STR58##                                         blue                    46                                                                                ##STR59##                                         blue                    47                                                                                ##STR60##                                         blue                    48                                                                                ##STR61##                                         blue                    49                                                                                ##STR62##                                         blue                    50                                                                                ##STR63##                                         blue                    51                                                                                ##STR64##                                         blue                    52                                                                                ##STR65##                                         blue                    __________________________________________________________________________

EXAMPLES 53 TO 56

The procedure of Examples 9, 10, 13 and 14 is repeated, except that the3- or 4-(2',3'-dibromopropionamido)benzenesulfonyl chloride is replacedby an equimolar amount of 3- or 4-chloroacetamidobenzenesulfonylchloride, affording the dyes indicated in column 2 of Table 6 which dyewool in the shades indicated in column 3.

                                      TABLE 6                                     __________________________________________________________________________                                                     Hue                                                                           on                           Ex.                                                                              Dye                                           wool                         __________________________________________________________________________    53                                                                                ##STR66##                                    blue                         54                                                                                ##STR67##                                    blue                         55                                                                                ##STR68##                                    blue                         56                                                                                ##STR69##                                    blue                         __________________________________________________________________________

EXAMPLES 57 TO 60

The procedure of Examples 17, 18, 21 and 22 is repeated, except that the3- or 4-(2',3'-dibromopropionamido)benzoyl chloride is replaced by anequimolar amount of 3- or 4-chloroacetamidobenzoyl chloride, affordingthe dyes indicated in column 2 of Table 7 below, which dye wool in theshades indicated in column 3.

                                      TABLE 7                                     __________________________________________________________________________                                                    Hue                                                                           on                            Ex.                                                                              Dye                                          wool                          __________________________________________________________________________    57                                                                                ##STR70##                                   blue                          58                                                                                ##STR71##                                   blue                          59                                                                                ##STR72##                                   blue                          60                                                                                ##STR73##                                   blue                          __________________________________________________________________________

EXAMPLE 61

6.62 parts of the dye of the formula (104) are dissolved in 50 parts ofwater at pH 7 by adding hydrochloric acid. A suspension of 2.9 parts of4-acetamidobenzenesulfonyl chloride in 40 parts of acetone is then addeddropwise at room temperature in the course of 10 minutes, during whichthe pH is maintained at a constant 7. Stirring overnight is followed byclarification, and the filtrate is brought to 13.5 with sodium hydroxidesolution and refluxed for one hour. It is then clarified at roomtemperature, brought to a pH of 7-8 with hydrochloric acid and sodiumchloride is added to it. The dye is filtered off with suction and washedwith sodium chloride solution. The moist dye paste is dissolved in 200parts of water, and 0.84 part of sodium bicarbonate is added. This isfollowed by the rapid dropwise addition of 2.76 parts of2,3-dibromopropionyl chloride at pH 7. After stirring overnight at pH 7,sodium chloride is added, and the dye is filtered off, washed withsodium chloride solution and dried at 60°-70°. 8.7 parts are obtained ofthe dye of the formula (111).

EXAMPLES 62 TO 68

Example 61 is repeated, except that the 4-acetamidobenzenesulfonylchloride is replaced by an equimolar amount of3-acetamidobenzenesulfonyl chloride or 4-acetamidobenzoyl chloride or3-acetamidobenzoyl chloride together with the dye of the formula (104)or by an equimolar amount of the formula (101), affording dyes of theformulae (112), (115), (116), (119), (120), (123) and (124).

EXAMPLES 69 TO 76

The procedure of Examples 61 to 68 is repeated, except that the2,3-dibromopropionyl chloride is replaced by an equimolar amount ofchloroacetyl chloride, affording the dyes of the formulae (143), (144),(145), (146), (147), (148), (149) and (150).

EXAMPLES 77 TO 93

The procedure of Examples 1, 2, 5, 6, 10, 12, 16, 18, 22, 24, 30, 33,34, 55 or 60 is repeated, except that the amine of the formula (101) isreplaced by an equimolar amount of one of the amines indicated in column2 of Table 8, affording the dyes indicated in column 3, which dye woolin the shades indicated in column 4.

    TABLE 8      Ex. Amine Dye Hue on wool       77  reddish blue      ##STR74##      ##STR75##      78  greenish blue     ##STR76##      ##STR77##      79  reddish blue     ##STR78##      ##STR79##      80  greenish blue     ##STR80##      ##STR81##      81  greenish blue     ##STR82##      ##STR83##      82  blue     ##STR84##      ##STR85##      83  blue     ##STR86##      ##STR87##      84  blue     ##STR88##      ##STR89##      85  blue     ##STR90##      ##STR91##      86  blue     ##STR92##      ##STR93##      87  blue     ##STR94##      ##STR95##      90  blue     ##STR96##      ##STR97##      91  blue     ##STR98##      ##STR99##      92  blue     ##STR100##      ##STR101##      93  greenish blue     ##STR102##      ##STR103##

DYEING EXAMPLE 1

4 parts of 80% acetic acid, 2 parts of the ammonium salt of the acidsulfuric ester of the adduct of a fatty amine (consisting of 30%hexadecylamine, 25% octadecylamine and 45% octadecenylamine and 7 moleequivalents of ethylene oxide) and also 4 parts of ammonium sulfate aredissolved in succession in 4,000 parts of water at 50°.

5 parts of the dye of the formula (103) obtained as described in Example2 are dissolved in 100 parts of hot water, and the solution is added tothe above dyebath. 100 parts of prewetted wool knitting yarn are thenintroduced, and the temperature of the bath is raised from 50° to 80° inthe course of 30 minutes. After 20 minutes of dyeing at 80°, thetemperature is raised to the boil, and dyeing is continued at the boilfor 90 minutes. Almost all the dye goes on the substrate. After the bathhas been cooled at 80°, the pH is increased from about 4.5 to apermanent 8.5 by adding ammonia solution, and the dyed material isaftertreated at that temperature for 20 minutes. Thorough rinsing withhot and cold water, acidification with 1 part of 80% formic acid,centrifuging and drying leaves a dark blue wool yarn having very goodwet and rub fastness properties and an excellent light fastness.

DYEING EXAMPLE 2

A wool fabric with an antifelting finish is impregnated with thepreparation described hereinafter and is squeezed off on a pad-mangle toa wet pick-up of 250%:

    ______________________________________                                        4       parts of Diaprint REG ® (acid-resistant thickener)                1       part of sulfamic acid                                                 0.2     part of thymol                                                        0.2     part of emulsifier                                                    94.6    parts of water                                                        100     parts.                                                                ______________________________________                                    

In a hot press the impregnated material is then contacted for 3 minutesat 100° to 105° under a pressure of about 0.5 kg/cm² with a transferpaper bearing a print pattern applied in a conventional manner with thedye of Example 3. After the wool fabric has been rinsed and dried itshows a corresponding blue print pattern having very good fastnessproperties.

DYEING EXAMPLE 3

A flannel fabric in chlorinated wool is impregnated on a padder manglewith the dye preparation described hereinafter and squeezed off to a wetpick-up of 100%:

    ______________________________________                                        50   parts of the dye of Example 8                                            300  parts of urea                                                            320  parts of Solvitose OFA ® at 4% (thickener)                           10   parts of a mixture of anionic fatty alcohol ether sulfate with                nonionic wetting agents                                                  10   parts of the levelling agent used in Dyeing Example 1                    10   parts of sodium metabisulfite                                            10   parts of 80% acetic acid                                                 290  parts of water                                                           1000 parts of padding liquor.                                                 ______________________________________                                    

The impregnated fabric is then rolled up and packed airtight and left inthat state at room temperature for 48 hours. After rinsing with coldwater the material is treated in a fresh bath with sufficient 24%ammonia as to give a pH of 8.5 and is maintained at 80° for 15 minutes.After rinsing in hot water it is finally soured off with 80% acetic acidand dried. The wool fabric shows a full blue shade having excellentfastness properties.

DYEING EXAMPLE 4

A flannel fabric of chlorinated wool is impregnated on a pad-mangle withthe dye preparation described hereinafter and squeezed off to a liquorpick-up of 100%:

    ______________________________________                                        50    parts of the dye of Example 1                                           300   parts of Solvitose OFA ® at 40% (thickener)                         20    parts of a mixture of anionic                                                 fatty alcohol ether sulfate with nonionic wetting agents                10    parts of the levelling agent used in Dyeing Example 1                   20    parts of 80% acetic acid                                                600   parts of water                                                          1000  parts of padding liquor.                                                ______________________________________                                    

The impregnated fabric is then introduced into a steamer and treatedwith saturated steam for 20 to 40 minutes. After rinsing with coldwater, the material is treated in a fresh bath with sufficient 24%ammonia solution as to give a pH of 8.5 and is maintained at 80° for 15minutes. After rinsing with hot water it is finally soured off with 80%of acetic acid and dried. The wool fabric shows a full blue shade havingexcellent fastness properties.

DYEING EXAMPLE 5

4 parts of 80% acetic acid, 2 parts of the ammonium salt of the acidsulfuric ester of the adduct of a fatty amine (consisting of 30%hexadecylamine, 25% octadecylamine and 45% octadecenylamine and 7 molesof ethylene oxide), and also 4 parts of ammonium sulfate are dissolvedin succession in 1,000 parts of water at 50°.

3 parts of the dye obtained as described in Example 18 are dissolved in100 parts of hot water, and the solution is added to the above dyebath.A circulation dyeing machine is entered with 100 parts of prewettedslubbing in muff form and the temperature of the bath is raised from 50to 97°-99° in the course of 30 minutes, and dyeing is continued at theboil for 90 minutes. Almost all the dye goes onto the substrate. Afterthe bath has been cooled down to 80°, the pH is raised from about 4.5 toa permanent 8.5 by the addition of ammonia solution, and the dyedmaterial aftertreated at that temperature. Thorough rinsing with hot andcold water, souring off with 1 part of 80% formic acid, centrifuging anddrying leaves a dark blue material having very good wet fastness andexcellent light fastness.

DYEING EXAMPLE 6

6 parts of 80% acetic acid, 3 parts of ammonium salt of the acidsulfuric ester of the adduct of a fatty amine (consisting of 30%hexadecylamine, 25% octadecylamine and 45% octadecenylamine and 7 molesof ethylene oxide) and also 6 parts of ammonium sulfate are dissolved insuccession in 1,000 parts of water at 50°.

3 parts of the dye obtained as described in Example 2 are dissolved in100 parts of hot water, and the solution is added to the above dyebath.A circulation dyeing machine is entered with 150 parts of prewettedloose wool, and the temperature of the liquor is raised from 50° to97°-99° in the course of 30 minutes, and dyeing is then continued at theboil for 90 minutes. Almost all the dye goes onto the substrate. Afterthe liquor has been cooled down to 80°, the pH is raised from about 4.5to a permanent 8.5 with the addition of ammonia solution, and the dyedmaterial is aftertreated at that temperature for 20 minutes. Thoroughrinsing with hot and cold water, souring off with 1 part 80% formicacid, centrifuging and drying leaves a blue substrate which has beendyed level in the fibre and has good wet and rub fastness and excellentlight fastness properties.

DYEING EXAMPLE 7

4 parts of 80% acetic acid, 2 parts of the ammonium salt of the acidsulfuric ester of the adduct of a fatty amine (consisting of 30%hexadecylamine, 25% octadecylamine and 45% octadecenylamine and 7 molesof ethylene oxide) and also 4 parts of ammonium sulfate are dissolved insuccession in 4,000 parts of water at 50°.

0.25 part of the dye obtained as described in Example 9 and 0.30 part ofthe yellow dye of the formula ##STR104## and 0.30 part of the red dye ofthe formula ##STR105## are dissolved in 100 parts of hot water, and thesolution is added to the above dyebath. 100 parts of prewetted woolfabric are then introduced, and the temperature of the bath is raisedfrom 50° to 80° in the course of 30 minutes. After 20 minutes of dyeingat 80°, the temperature is raised to the boil, and dyeing is thencontinued at the boil for 90 minutes. Almost all the dye goes onto thesubstrate. After the bath has been cooled down to 80°, the pH is raisedfrom about 4.5 to a permanent 8.5 with the addition of ammonia solution,and the dyed material is aftertreated at that temperature for 20minutes. Thorough rinsing with hot and cold water, souring off with 1part of 80% formic acid, centrifuging and drying leaves a dark brownwool fabric which has been dyed level in the fibre and has very good wetand rub fastness and excellent light fastness properties.

DYEING EXAMPLE 8

4 parts of 80% acetic acid, 2 parts of the ammonium salt of the acidsulfuric ester of the adduct of a fatty amine (consisting of 30%hexadecylamine, 25% octadecylamine and 45% octadecenylamine and 7 molesof ethylene oxide) and also 4 parts ammonium sulfate are dissolved insuccession in 1,000 parts of water at 50°.

0.6 part of the dye obtained as described in Example 2, 0.09 part of theyellow dye of the formula ##STR106## and 0.2 part of the red dye of theformula ##STR107## are dissolved in 100 parts of hot water, and thesolution is added to the above dyebath. A circulation dyeing machine isentered with 100 parts of prewetted slubbing in muff form, and thetemperature of the bath is raised from 50° to 97°-99° in the course of30 minutes, and dyeing is then continued at the boil for 90 minutes.Almost all the dye goes onto the substrate. After the bath has beencooled down to 80°, the pH is raised from about 4.5 to a permanent 8.5with the addition of ammonia solution, and the dyed material isaftertreated at that temperature for 20 minutes. Thorough rinsing withhot and cold water, souring off with 1 part of 80% formic acid,centrifuging and drying leaves a grey material having very good wetfastness and excellent light fastness properties.

I claim:
 1. A process for the trichromatic dyeing or printing of naturaland synthetic polyamide materials with dye mixtures, which comprisesusing a fibre-reactive formazan dye of the formula ##STR108## where B isan aliphatic or sulfo-free aromatic bridge member, R isα,β-dihalopropionyl, α-haloacryloyl or haloacetyl, T₁ is halogen, X ishalogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, cyano or nitro, Y is --CO-- or--SO₂ --, Z is nitrogen or --C--T₂, T₂ is halogen, hydrogen, C₁ -C₄alkylthio, cyano, formyl or C₁ -C₄ alkylsulfonyl, m is 1, 2 or 3, n is0, 1 or 2, q is 0 or 1, and r and s are each either 0 or 1 but never thesame as each other, together with a fibre-reactive sulfo-containingred-dyeing azo dye and a fibre-reactive sulfo-containing yellow- ororange-dyeing azo dye.
 2. A process according to claim 1, wherein theyellow- or orange- and red-dyeing dyes each contain as thefibre-reactive group a halotriazine or a halopyrimidine group or aα-β-dihalopropionyl or α-haloacryloyl.
 3. A process according to claim1, wherein the yellow- or orange- and red-dyeing dyes contain as thefibre-reactive group difluorochloropyrimidinyl, α-β-dihalopropionyl, orα-haloacryloyl.
 4. The process according to claim 3, wherein thefibre-reactive group includes 2,4-difluoro-5-chloropyrimidinyl.
 5. Theprocess according to claim 3, wherein the fibre-reactive group includesα,β-dibromopropionyl.
 6. The process according to claim 3, wherein thefibre-reactive group includes α-bromoacryloyl.
 7. The process accordingto claim 1, wherein the polyamide material is wool.